CN1278856A

CN1278856A - Fuel composition and blend

Info

Publication number: CN1278856A
Application number: CN98811087A
Authority: CN
Inventors: S·E·泰勒
Original assignee: BP Oil International Ltd
Current assignee: BP Oil International Ltd
Priority date: 1997-11-13
Filing date: 1998-11-13
Publication date: 2001-01-03
Also published as: DE69802003D1; GB0009218D0; GB2346154A; ATE206744T1; BG104518A; WO1999025793A1; AU733400B2; KR20010031963A; PL340304A1; GB2346154B; HUP0004736A3; JP2002506085A; MXPA00004673A; AU1164199A; CA2309061A1; EP1029026B1; NO20002471D0; NO20002471L; ID24624A; TR200001227T2

Abstract

A fuel composition having reduced tendency to discoloration at high temperatures comprises kerosine and/or is a jet fuel, and also comprises a cyclic compound comprising m units of the formula 1a. and n units of the formula (Ib) joined together to form a ring, wherein Y is a divalent bridging group which may be the same or different in each unit; R0 is H or (C1-C6) alkyl; R5 is H or (C1-C60) alkyl; and j is 1 or 2; R3 is hydrogen, a hydrocarbyl or a hetero-substituted hydrocarbyl group; each of R1, R2 and R4, which may be the same or different, is hydroxyl, hydrogen, hydrocarbyl or hetero-substituted hydrocarbyl, with the proviso that at least one of R1, R2, R4 is hydroxyl, and m+n is 4 to 20, m is 1-8 and n is at least 3 and preferably either R1 is hydroxyl and R2 and R4 are independently either hydrogen, hydrocarbyl or hetero-substituted hydrocarbyl, or R2 and R1 are hydroxyl and R1 is either hydrogen, hydrocarbyl or hetero-substituted hydrocarbyl; and m+n is from 4 to 20, m is from 1 to 8 and n is at least 3.

Description

Fuel composition and mixture

The present invention relates to fuel composition, particularly aviation is with the fuel composition of fuel composition or burning usefulness and be used for wherein mixture.

In high-speed aircraft, comprise civil and military, liquid fuel produces power through burning, but also circulates in the aircraft as heat exchange fluid, going out to remove the unnecessary heat that produces under this kind high speed, for example in the lubricating oil.Therefore, fuels tend is kept at high temperature for a long time, and this will cause variable color and decomposition, generates soluble coloured product and insoluble product such as colloid, precipitation and particulate matter; Insoluble product can form the settling that reduces heat-exchange capacity, and the possibility blocking filter, thereby constitutes the potentially dangerous of forfeiture power.The coloured by product of solubility diminishes outward appearance and shows certain decomposition has taken place.Variable color and so on problem can be by due to ever-present phenols, naphthenate and sulphur compound and/or the metal in the fuel.

In some oil-burning apparatus, for example boiler and slow hot digestion device, Aga type for example, kerosene stock enters into combustion chamber and burning therein via narrow metal supply-pipe.These pipe fittings are very near apart from hot chamber, are enough to be heated quite high temperature, thereby cause the danger of fuel thermal destruction in the pipe, especially in pipe under the situation of slow and high residence time of feeding rate.This kind degraded can generate and reduce flow rate and finally stop the mobile solid precipitation, thereby causes burning to stop.For overcoming this problem, the manufacturers of this kind equipment advises its user cleaning in per at least 6 months once coking in these pipe fittings or the solid deposits of other materials for many years always.

USP5478367 has described and added the unsaturated polyamine derivative dispersion agent that replaces in diesel oil or jet fuel, to reduce the particulate emission after burning and to reduce fouling, that is, and the deposition of infusible precipitate.This macrocylc compound preferably comprises the N=C-N-C=O group, particularly comprises condensed ring, for example prepared in reaction by alkyl (as aliphatic alkyl) succinyl oxide and polyalkylene amine.

Canadian Patent discloses 2067907 and has described the method that adds azanol in the cut jet fuel, so that their high temperature resistant degradeds.

USP5468262 has described and added thermal stabilization additive in jet fuel, and it is by polyamines, aldehyde and the phenol generation condenses that reacts, and then reacts with the succinyl oxide of the unsaturated group that contains polyolefin derivative and to make.This additive is effective in the consumption level of 0.2wt%.

EP-A-678568 has described and added anti-sludging agent in jet fuel, and it is (sulfo-) phosphonic derivative.

Have now found that a kind of improvement thermal stabilization additive that is used to contain kerosene stock and jet fuel, it is the oil soluble macromole that comprises hydroxyl-carboxylic acid functional.

In view of the above, the invention provides a kind of fuel composition, it comprises kerosene and/or is a kind of jet fuel, also comprises a kind of ring compound, and this ring compound comprises the unit of m formula I a,

And the unit of n general formula (I b), The two links together and constitutes a ring,

Wherein Y is a divalent bridging group, and they can be identical or different in each unit;

R ⁰Be H or (C ₁～C ₆) alkyl; R ⁵Be H or (C ₁～C ₆₀) alkyl; J is 1 or 2;

R ³Be hydrogen, alkyl or the assorted hydrocarbyl group that replaces; R ¹, R ²And R ⁴Can be identical or different, each is hydroxyl, hydrogen, alkyl or the assorted alkyl that replaces, condition is R ¹, R ², R ⁴In at least 1 be hydroxyl, and m+n is 4～20, m is 1～8, n is 3 at least, and preferably, perhaps R ¹Be hydroxyl and R ²And R ⁴Be hydrogen, alkyl or the assorted alkyl that replaces, perhaps R independently ²And R ⁴Be hydroxyl and R ¹Be hydrogen, alkyl or the assorted alkyl that replaces; And m+n is 4～20, and m is 1～8, and n is 3 at least.

This ring compound preferably has the logical formula I compound of following ring texture.(I)

Y wherein ¹And Y ²Be divalent bridging group, they can be identical or different; R ³Be hydrogen, alkyl or the assorted hydrocarbyl group that replaces; R ¹, R ²And R ⁴Can be identical or different, each is hydroxyl, hydrogen, alkyl or the assorted alkyl that replaces, condition is R ¹, R ², R ⁴In at least 1 be hydroxyl, and m+n is 4～20, m is 1～8, n is 3 at least.

When being present in this ring more than 1 Whitfield's ointment unit and going up (, m＞1), this Whitfield's ointment and phenol unit can randomly distribute, although this and be not precluded within on some ring and may exist several Whitfield's ointments unit to connect into a string possibility.Therefore, but this m and n unit block connection, and/or random connection.

In formula I, Y ¹And Y ²Can be alkyl bridged group or the assorted hydrocarbyl group that replaces, perhaps Y independently of one another ¹With Y ²The highest 50mol% of group summation is a heteroatoms.Alkyl bridged group chain preferably aliphatic series and that have 1～4 carbon atom; Preferably, this group has general formula (CR ⁷R ⁸) _d, (CHR for example ⁸) _d, R wherein ⁷And R ⁸Can be identical or different, each represents hydrogen or alkyl, 1～6 carbon atom for example, it is concrete that d is 1～4 integer as methyl or ethyl, preferably 2 or, especially 1; Advantageously, this group has general formula (CHR ⁸) _d, R wherein ⁸Meet top regulation and preferably methyl or, hydrogen especially.Y ¹And/or Y ²Also can represent the assorted hydrocarbyl group that replaces, wherein heteroatoms for example is O, S or NH, and they are embedded in carbon atom chain, for example among the chain of 2～4 carbon atoms, for example become CH ₂OCH ₂, CH ₂SCH ₂Or CH ₂NHCH ₂Y ¹With Y ²The highest 50mol% of group summation can be a heteroatoms, for example O or NH or, S especially, heteroatoms for example accounts for 1～50mol% of described group, especially 8～20mol%.Preferably, Y ¹And Y ²It is the compound sulfur-bearing not of alkyl and formula I.

R ¹, R ²And R ⁴In each representation hydroxy, hydrogen, alkyl or the assorted alkyl that replaces, condition is R ¹, R ², R ⁴In at least 1 be hydroxyl.Therefore, these 3 groups are representation hydroxy all, and as in the Phloroglucinol derivative, perhaps 2 is hydroxyl, as resorcinol derivatives (that is, the compound of general formula I comprises the Resorcinol aryl), and perhaps 1, as in the phenol derivatives.Preferably, perhaps R ¹Be hydroxyl and R ²And R ⁴Be hydrogen (this is preferred), alkyl or the assorted alkyl that replaces, perhaps R independently ²And R ⁴Be hydroxyl and R ¹Be hydrogen, alkyl or the assorted alkyl that replaces.

About R ¹～R ⁵And R ⁸, term " alkyl " comprises (C ₁～C ₆₀) alkyl, as the tertiary butyl, tert-pentyl, sec-butyl, sec.-propyl, octyl group, nonyl, dodecyl and octadecyl.Alternatively, hydrocarbyl group can for example by polyethylene, polypropylene, polybutene, perhaps be derived by polyolefin copolymer by polyolefin derivative, for example by ethylene/propene copolymer, is preferably derived by polyisobutene.The alternate source comprises isoprene-butadiene, styrene-isoprene or styrene-butadiene block copolymer, as those disclosed among the WO96/40846, perhaps molecular weight is at 1500～2500 or 7500 ethylene-propylene and ethene-1-Butylene copolymer, and is for example disclosed in US 5567344 and US 5578237.Also can use the mixture of all above-claimed cpds.The heteroatoms that hydrocarbyl group had of any assorted replacement preferably-O-or=NH, they are embedded in the middle of the carbon atom chain, for example become the alkoxyl group-alkyl group of 2～20 carbon atoms.R ¹～R ⁵In each can be as following in other respects at R ³Described such.

R ¹, R ²Or R ⁴The hydrocarbyl group of representative generally has 1～14, for example 1～6 carbon atom and preferably saturated, especially alkyl group, for example methyl, ethyl, propyl group, butyl or hexyl groups.The assorted hydrocarbyl group that replaces has at least 1, and for example 1～3,1 heteroatoms especially, for example O, S or NH, they for example are embedded in 2～20, or in the middle of the carbon atom chain of 2～6 carbon atoms, as at the alkoxyl group alkylidene group, as in the ethoxyethyl group.

R ³Be hydrogen, alkyl or the assorted hydrocarbyl group that replaces.Preferably, the R at least in generalformula ³In the group, R ³Be alkyl or the assorted alkyl that replaces, especially in this molecule, have under the situation of n this type of group.This hydrocarbyl group can be alkyl, alkenyl, cycloalkyl, aryl, aralkyl, and comprises at least 1 in the chain, especially at least 4, and perhaps at least 8 carbon atoms, for example 4～40 carbon atoms, particularly 8～20 carbon atoms.

The alkyl of preferred line style or side chain as 8～24 or 8～20 carbon atoms, for example is decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, lauryl, myristyl, stearyl, palmityl, the propylene tetramer; Or alkenyl, 6～24 carbon atoms for example are as oil base; Or cycloalkyl, 5～8 carbon atoms for example are as cyclohexyl; Aryl, 6～24 carbon atoms for example, as phenyl, tolyl and have the alkyl phenyl of 6～16 alkyl carbon atoms, as dodecylphenyl, and aralkyl, for example 7～26 carbon atoms, for example benzyl, and even the benzyl that the alkyl with 6～16 alkyl carbon atoms replaces, for example dodecylbenzyl.R ³Also can represent the polymerization alkyl,, particularly derive by the alkene of one or more 2～6 carbon atoms such as ethene, propylene, butylene, iso-butylene for example by the polyolefine group; This polymeric groups can be derived by polyethylene, polypropylene, polybutene and ethylene-propylene copolymer or polyisobutene (latter is preferred).Polymeric R ³The molecular weight of group can be 300～6000, for example 500～2000.In the compound of formula I, with the R in a part ³Can differ from one another.

In the compound of formula I, m is 1～8, for example 1～4, especially 2 or, particularly 1, n is 3 at least simultaneously, for example is 3～10, particularly 5～9, especially 6～8.The m+n sum is 4～20, preferably 5～10, particularly 7～9, for example 6 or 8, or the numerical value of m+n equals the mixture of 6 and 8 compound.Preferably, m be 1 and m+n be 5～10.

In preferred bigcatkin willow aromatic hydrocarbons (salixarenes), Y, Y ¹Or Y ²Be CH ₂R ¹It is hydroxyl; R ²And R ⁴Be hydrogen, alkyl or the assorted alkyl that replaces independently; R ³Be alkyl or the assorted alkyl that replaces; R ⁰Be hydrogen; R ⁵Be hydrogen or 6～50 carbon atoms, preferred 4～40 carbon atoms, the more preferably alkyl group of 6～25 carbon atoms; J be 2 or, preferably 1; The numerical value of m+n is 5 at least, preferably is 6 at least, and representative value is 8 at least, and wherein m is 1 or 2, preferably 1.

More preferably, R ²And R ⁴Be hydrogen; R ³Be alkyl, preferably greater than 4, more preferably greater than the alkyl of 9 carbon atoms; R ⁵Be hydrogen; M+n is 6～12; M is 1 or 2.

In preferred compound, R ²And R ⁴Be hydrogen, m is 1 or 2, and n is 5,6 or 7, and m+n is 6 and/or 8, R ¹Be hydroxyl, R ³Be the alkyl of 8～20 carbon atoms, as dodecyl or octadecyl, or polyisobutenyl.

For simplicity, the compound of formula I is known as " bigcatkin willow aromatic hydrocarbons " in this article.

The summary of relevant phenol Polycyclic aromatic hydrocarbons (calixarenes), the reader can be referring to " the supramolecular chemistry monograph " of C DavidGutsche, series editor--J Fraser Stoddart, Royal Institute of Chemistry publishes, and 1989.Having " phenol Polycyclic aromatic hydrocarbons " that one or more hydroxyls substitute base comprises with phenol Polycyclic aromatic hydrocarbons (homocalixarenes), oxa-phenol Polycyclic aromatic hydrocarbons (oxacalixarenes), with oxa-phenol Polycyclic aromatic hydrocarbons (homooxacalixarenes) and creosote Polycyclic aromatic hydrocarbons (heterocalixarenes).

Bigcatkin willow aromatic hydrocarbons can be by proper amt Whitfield's ointment (or carboxylicesters), the optional phenol and the carbonyl compound that replaces of optional replacement, the latter is aldehyde such as formaldehyde or acetaldehyde preferably, exists next to react at alkali and optional catalyzer and prepare.This reaction can be implemented in the presence of sulphur, comprises the words of combined sulfur if wish the compound of formula I.

Bigcatkin willow aromatic hydrocarbons can be by comprising the following steps the method preparation: with 50wt% or more under the dilution condition of high solvent, in the presence of basic catalyst, (II is a) and the compound of (II b) for general formula With general formula O=CHR ⁶Aldehyde and optional sulphur react together; R wherein ⁰～R ⁶And j is according to the regulation of front." 50wt% dilutes (degree) " is meant that after the total overall reaction thing all added, solvent accounted for the 50wt% at least of reaction soln.Preferred this solvent accounts for the 80wt% at least of reaction soln, more preferably 90wt% at least.

Preferred basic catalyst is alkali metal hydroxide such as sodium hydroxide, potassium hydroxide and lithium hydroxide.Sodium hydroxide is most preferred.

Why reaction mixture needs high dilution, is in order to ensure the generation ring-type, rather than thread-like molecule; When extent of dilution is significantly less than 50wt%, only generate thread-like molecule.Yet even under the high dilution condition, the part in the product still can comprise thread-like molecule.Thread-like molecule also can by general formula (I a) and the unit of (I b) form, only the end of molecule is not to be connected to each other to a ring, but each end has the end group that is independently selected from down one of array structure:

In thread-like molecule, unit number m+n sum is 2～20, and m is 1～8, and n is 1 at least.Another aspect of the present invention provides above-mentioned general formula, and (II a) and (II b) and general formula O=CHR ⁶Aldehyde and the reaction product of optional compounds such as sulphur; R wherein ⁰～R ⁶By the regulation of front, this reaction product comprises the general formula that comprises of 20wt% at least, and (I a) and (I b) unitary ring compound and be no more than the line style form of 80% described compound.Preferably, annular form accounts at least 40% of entire reaction product, and more preferably at least 60%, 80wt% at least most preferably.

This fuel composition, for example the jet fuel composition also can comprise acyclic, i.e. the compound of the general formula 1a/1b I of line style form, that is, its structural unit is shown in formula I, however the end of the chain is generally phenol and/or Whitfield's ointment unit.

The present invention also provides at least a kind of this class " bigcatkin willow aromatic hydrocarbons " reducing the jet fuel composition and containing application aspect the kerosene stock composition heated discoloration.

Preferred additives is dodecyl-bigcatkin willow-phenol ring [8] aromatic hydrocarbons (dodecyl-salicvlic calix[8] arene), it is 1 bigcatkin willow [8] aromatic hydrocarbons, wherein comprise phenol units and 1 Whitfield's ointment unit that 7 dodecyls replace, link together by methylene bridge therebetween, for example be present in the following compd A reaction product like that.Another kind of preferred compound is to have 2 Whitfield's ointment groups and 6 unitary bigcatkin willow aromatic hydrocarbons of 4-dodecylphenol.

The amount that this additive exists in composition is a benchmark with the weight of composition such as jet fuel composition, is 1 at least, is 5ppm at least, for example 1～1000,5～1000, for example 5～500, especially 5～200 or 10～100ppm.The fusion of this additive and jet or other fuel compositions can be implemented by its conc forms in solution, the solution of 20～80%w/w in aliphatic aromatic hydrocarbons for example, thus perhaps it can directly add the solution that obtains in fuel.Can have more than a kind of bigcatkin willow aromatic hydrocarbons to exist, for example 2～4 kinds, especially those only on the two numerical value one of at least of m and n, particularly only different on the numerical value of n.

Said composition can comprise jet fuel.Said composition can comprise kerosene, particularly in jet fuel.The main component of jet fuel itself normally the boiling point under the atmospheric pressure 150～250 ℃ medium boiling point fraction, and this fuel is kerosene normally, this kerosene can with gasoline and randomly primary flash distillate carry out fusion, become the mixture between gasoline and the kerosene.Jet fuel can comprise the mixture of gasoline and primary flash distillate, for example by 20～80: 80～20, and 50～75: 50～25 weight ratio for example, such part by weight also can be used for the mixture of gasoline and kerosene.The trade mark of military jet fuel is JP4～8, JP4 for example, that is, and 65% gasoline/35% primary flash distillate (by U.S.'s military products standard (MIL 5624G)); JP5 is similar to JP4, but flash-point is higher; JP7, the high flash point superior kerosene is exclusively used in senior supersonic plane; And JP8, the kerosene of a kind of Jet of being similar to A1 (pressing MIL 83133C).The civil version jet fuel generally is a kerosene type fuel, and the trade mark is Jet A or Jet A1.The boiling point of this jet fuel can be at 66～343 ℃ or 66～316 ℃ (150～650 °F, for example 150～600 °F), initial boiling point is at 149～221 ℃, for example 204 ℃ (300～430 °F, for example 400 °F), ℃ (430～600) and 90% boiling point are at 260～343 ℃ (500～650 °F) in 22l～316 for 50% boiling point, and api gravity is 30～40.The jet fuel oil boiling point that turbo jet engine uses can be at 93～260 ℃ of (200～500) (ASTM D1655-59T).Relevant aviation can be referring to " aviation is worked in coordination with research joint committee with the fuel performance handbook, and CRC reports number 530 (Incorporated Institution of Automobile Engineers, Warrendale, PA, USA, 1983) with the further details of fuel; The military fuel of the relevant U.S. is referring to " vaviation turbine fuel army specifications ", MIL-T-5624P.

Jet fuel can be a virgin kerosene, randomly adds gasoline, wherein generates or promotion coloured product of generation and/or sedimentary composition but preferably passed through to purify to reduce.Aromatic hydrocarbons, alkene and mercaptan are arranged in the middle of these compositions.For example, this fuel can utilize purification to reduce its mercaptans content, and for example Merox fuel and solid copper sweetening process fuel perhaps reduce its sulphur content, for example hydrofining fuel or Merifined fuel.Merox fuel is made by mercaptan is implemented oxide treatment, have low " mercaptan sulphur content " (for example being lower than 0.005wt%S), as 0.0001～0.005%, yet, its disulphide sulphur content is higher (for example to be up to 0.4% or the highest 0.3wt%S, for example 0.05～0.25, for example 0.1～2%); Its aromatic hydrocarbons (as phenols) and olefin(e) centent then almost do not change.The hydrofining jet fuel is a material fuel through hydrogenation to remove some sulphur compound at least, mercaptan for example, and under rigor condition, make aromatic hydrocarbons and alkene change the fuel of stable hydrocarbon into; The hydrofining jet fuel has low-down sulphur content (for example being lower than 0.01wt%S).Merifined fuel is through extracting with organic extractant to reduce or to remove its sulphur compound and/or contain the fuel that phenol is obtained.This jet fuel also may comprise metal, or with after metallic conduit contacts or come from the crude oil band; The example of these metals is copper, nickel, iron and chromium, and general content is less than 1ppm, for example in the scope of 10～150ppb.Merox and hydrofining fuel are preferred, all can be used in JP 4～8 jet fuels.

This fuel that comprises kerosene also can be used as burning fuel, in particular for non-driving purposes, for example be used for generating, generation steam and heating, especially for buildings and boiling, for example described above.This fuel is particularly suitable for all boilers as described above and slow cooking device, wherein exists the situation that fuel is subjected to partial preheating before its burning.This class A fuel A is known as illuminating kerosene, its physicals can with jet fuel such as the virgin kerosene based on kerosene described above, perhaps through modification identical with the kerosene that reduces at least a kind of content in its above-mentioned aromatic hydrocarbons, alkene and the sulphur compound.This fuel also may comprise metal described above.

Fuel composition of the present invention comprises the ring compound of general formula 1a/1b or I and can comprise at least a kind of conventional additive, for example be generally used for jet fuel or burning with fuel, for example oxidation inhibitor, inhibiter, dispersion agent/washing composition (particularly (face is described as follows) under the situation of hydroxycarboxylic acid being arranged), especially, every kind consumption is at 1～1000ppm, for example 20～200ppm." bigcatkin willow aromatic hydrocarbons " additive of formula I can be present in the composition, particularly is used with dispersion agent; Particularly those are added into as automobile fuel or aviation and are used for the known dispersion agent of dispersible solid in the fuel with fuel and so on this dispersion agent.This type of dispersion agent generally has polymerization master carbochain, has nitrogenous side group on it, can be primary, the second month in a season or uncle's nitrogen side group, and they are present in ring-type or the non-member ring systems, especially in amine, acid amides or imide group, particularly in the cyclic imide group.This dispersion agent also can comprise 1～5 polymer chain by the nitrogen-containing group bridging.The example of this type of dispersion agent is the reaction product of polyisobutylene succinic anhydride (PIBSA) and polyamine.This class dispersion agent is to be used for making particulate matter to be distributed to the known compound of non-aqueous system such as hydro carbons system." bigcatkin willow aromatic hydrocarbons " can be between 99: 1～10: 90, between especially 30: 70～70: 30 to the weight ratio of dispersion agent.These additives and fuel composition preferably do not contain ash content substantially.Illuminating kerosene except that comprising formula I or I a/ I b compound, does not generally contain above-mentioned additive.

The fuel composition of the present invention that contains formula I, I a, I b compound has the thermostability of improvement, be reflected in its heated discoloration and/or produce in solid tendency (at isothermal corrosiveness and oxidation test (ICOT is according to ASTM D4871)) and the reduction that fuel itself is compared.In some cases, the combination of generalformula and some other alpha-hydroxy carboxylic acid derivatives can be given the stability that some fuel further improves, promptly than independent use the two one of better.This kind synergistic effect shows in the combination of Merox fuel formula of I, I a, I b and hydroxycarboxylic acid.

Therefore, in preferred embodiments, the present invention also provides a kind of mixture, and it comprises among formula I, I a, the I b at least a kind of compound and has at least 1 hydroxycarboxylic acid that contains the chain of at least 8 carbon atoms (being different from described compound) with at least a kind.The present invention also provides a kind of fuel composition, it comprises described mixture, and contain kerosene stock and/or a kind of jet fuel, the latter is a Merox fuel, such composition especially is provided, that is, it is in the ICOT test of carrying out according to ASTM D4871, it is 80～120mg settling every liter of fuel, particularly 80～105mg/l that the average deposition thing generates tendency.

In mixture of the present invention, the weight ratio of the compound of formula I, I a, I b (c) and hydroxycarboxylic acid is generally 10～90: 90～1, especially 30～85: 70～15, particularly 35～65: between 65～35.The content of this mixture in fuel is generally 10～1000ppm, for example 30～200ppm.

This hydroxycarboxylic acid comprises at least 1 oh group altogether, and for example 1～4, for example 2 or 3, but preferred 1 oh group.It usually comprises and is positioned at, with respect to for the carbon atom of hydroxy-acid group bonding, oh group on α, β or the gamma carbon, and can randomly have the oh group that one or more are arranged in other positions of molecule: preferably, this unique oh group is positioned at α, β or γ in the molecule, especially the β position.This alcohol acid can have general formula,

R wherein ¹¹And R ¹³One of representation hydrocarbyl and another represent hydrogen or organic group, R ¹⁰, R ¹²And R ¹⁴Can be identical or different, the organic group that each is represented hydrogen or passes through carbon or heteroatoms O, N or S bonding, condition is R ¹⁰～R ¹⁴In at least 1, preferably only have 1 representative to contain the organic group of at least 8 carbon atom carbochains.The example of the organic group by carbon atom bonding is alkyl, cycloalkyl, alkenyl, aralkyl or aryl, for example the front is described at R3, especially the alkyl group of 8～3000 carbon atoms, 8～24 carbon atoms particularly, especially dodecyl, octadecyl, and 50～3000 carbon atoms, for example polyolefin-based, as by the polyisobutene deutero-.The example of the organic group by nitrogen atom bonding is to have for example amino group of the long chain hydrocarbon groups group of 8～24 carbon atoms, perhaps by having 8～3000 carbon atoms, long-chain carboxylic acid as 8～24 carbon atoms, as lipid acid, picture stearic acid and palmitinic acid institute deutero-amido, imino group, perhaps have 50～3000 carbon atoms, for example come free polyisobutene deutero-carboxylic acid derivative, for example polyolefin-based among the PIBSA.Especially, R ¹¹Preferred representation hydroxy/or hydrogen, R ¹⁰Represent hydrogen or at least 8 carbon atoms, the long chain hydrocarbon groups group of 8～24 or 50～3000 carbon atoms especially, R ¹²Represent alkyl such as the methyl or the ethyl of hydrogen or 1～6 carbon atom, R ¹³Representation hydroxy or hydrogen, R ¹⁴Represent hydrogen or have amino, amido or imino group or the long-chain one or the diacyl group, particularly long-chain succinimide of long-chain aliphatic group, for example PIBSA. especially, R ¹⁰Or R ¹⁴Comprise long-chain aliphatic group but be not that the two all comprises.The preferred example of hydroxycarboxylic acid is N (long acyl) derivative of following acid: beta-hydroxy amino acid; for example Serine and Threonine and long chain hydrocarbon groups alpha hydroxy acid, for example 1-hydroxy-dodecanoic acid, 1-hydroxy-palmitic acid and 1-oxystearic acid, 1-hydroxyl polyisobutenyl-1-carboxylic acid (deriving) by PIB aldehyde.

To further specify the present invention in conjunction with the following example now.

Compound

A. the preparation of dodecyl-bigcatkin willow-phenol ring [8] aromatic hydrocarbons

In 5L flange flask (flange flask), add following ingredients: 234.5g dodecane phenol (0.87mol, 1 equivalent)

17.25g Whitfield's ointment (0.125mol, 0.152 equivalent)

60g paraformaldehyde (2.00mol, 2.3 equivalents)

52.5g10M sodium hydroxide (40% aqueous solution) (0.525mol, 0.63 equivalent)

2kg dimethylbenzene (solvent)

Subsequently, set up reaction unit, comprise this 5L flange flask, blind flange and anchor clamps, have overhead, Dien-Rodney Stark couch water trap and the sleeve surface condenser (double surfacecondenser) of paddle and PTFE (tetrafluoroethylene) stir shaft seal cartridge.Reactor content is heated by electrically heated cover/thermopair/Eurotherm temperature controlling system.The glassware of this section below the condenser carries out thermal insulation protection with glass wool from extremely just beginning more than the lucky heating mantles.

Reaction mixture is heated to 90 ℃ rapidly, and temperature raises very lentamente with about 1 ℃ of per speed of 10 minutes subsequently.Collect water (77mL) in the time of 7h, temperature has reached 140 ℃ when this terminal point.Then, allow the compound cool overnight, (139 ℃) 2.5h again refluxes.Then, isolate the 100ml brown solution of generation, and drive xylene solvent out of with rotatory evaporator.The brown residue shows through gpc analysis, exists as main component: 26%1: 7 Whitfield's ointment: the Whitfield's ointment of dodecyl ring compound and 25%1: 5: dodecyl ring compound and 24～40% unreacting materials.

B.N (polyisobutenyl succinyl-) Serine

Example 1～3 mixture

Prepared respectively 75: 25,50: 50 and the compd A of 25: 75 weight ratios and the mixture of B.

Jet fuel

D．Merox

E．USAF?POSF?3119?Merox

F．USAF?POSF?2926?Merox

G．Merox

H. hydrofining fuel

Fuel D～H carries out average deposition thing that ICOT test obtained by ASTM D4871 and generates tendency and be respectively, and 99.4,89.4,74.3,110.5 and every liter of fuel of 96mg settling.

The ICOT test

This test is basically described in ASTM D4871.Test relates at 180 ℃ carries out the thermal treatment of 5h to 100mL fuel (add or not doping, be generally 4 batch of materials, comprising basic fuel as a comparison case), and air passes through fuel continuously with the flow velocity of 150mL/min around here.At the terminal point of this test, allow fuel cooling and leave standstill 24h before the filtration, filter by preweighted 0.45 μ m Millipore filtration medium then, and take by weighing any sedimental weight, be accurate to ± 1mg.Mensuration can leach precipitation and these 2 numerical value of gummy precipitation, and the settling total content is these two sum.The result is expressed as %ICOT efficient, that is, and and 100 * [the settling weight difference of Comparative Examples-sample]/Comparative Examples settling weight; Therefore this efficient be to adopt additive can obtain the tolerance that much settlings reduce.

Table 1

Fuel	Additive	ppm	ICOT% efficient
Fuel	Additive	ppm	ICOT% efficient	????D	????B	100	????68
????D	????A	100	????85	????D	????B	100	????68
????D	????A	100	????85	????D	A∶B	75∶25	????97
????D	A∶B	50∶50	????97	????D	A∶B	75∶25	????97
????D	A∶B	50∶50	????97	????D	A∶B	25∶75	????93

Table 2

Fuel	Additive	ppm	ICOT% efficient
Fuel	Additive	ppm	ICOT% efficient	????E	????B	100	????(4)
????E	????A	100	????35	????E	????B	100	????(4)
????E	????A	100	????35	????E	A∶B	75∶25	????40
????E	A∶B	50∶50	????54	????E	A∶B	75∶25	????40
????E	A∶B	50∶50	????54	????E	A∶B	25∶75	????17

Table 3

Fuel	Additive	ppm	ICOT% efficient
Fuel	Additive	ppm	ICOT% efficient	????F	????B	100	????(4)
????F	????A	100	????46	????F	????B	100	????(4)
????F	????A	100	????46	????F	A∶B	75∶25	????33
????F	A∶B	50∶50	????29	????F	A∶B	75∶25	????33
????F	A∶B	50∶50	????29	????F	A∶B	25∶75	????25

Table 4

Fuel	Additive	ppm	ICOT% efficient
Fuel	Additive	ppm	ICOT% efficient	????G	????B	?100	????15
????G	????A	?100	????69	????G	????B	?100	????15

Table 5

Fuel	Additive	ppm	ICOT% efficient
Fuel	Additive	ppm	ICOT% efficient	????H	????B	100	????33
????H	????A	?100	????61	????H	????B	100	????33
????H	????A	?100	????61	????H	A∶B	75∶25	????40
????H	A∶B	50∶50	????38	????H	A∶B	75∶25	????40

Claims

1. fuel composition, it comprises a kind of fuel, and the latter comprises kerosene and/or is a kind of jet fuel, also comprises a kind of ring compound, and this compound comprises the unit of m formula I a, And the unit of n general formula (I b) The two links together and constitutes a ring,

R ³Be hydrogen, alkyl or the assorted hydrocarbyl group that replaces;

R ¹, R ²And R ⁴Can be identical or different, each is hydroxyl, hydrogen, alkyl or the assorted alkyl that replaces, condition is R ¹, R ², R ⁴In at least 1 be hydroxyl, and m+n is 4～20, m is 1～8, n is 3 at least.

2. the composition of claim 1, wherein this compound is the compound with the logical formula I of following ring texture, Y wherein ¹And Y ²The regulation that meets relevant Y.

3. claim 1 or 2 composition, wherein, perhaps R ¹Be hydroxyl and R ²And R ⁴Be hydrogen, alkyl or the assorted alkyl that replaces, perhaps R independently ²And R ⁴Be hydroxyl and R ¹Be hydrogen, alkyl or the assorted alkyl that replaces.

4. the composition of claim 3, wherein R ¹Be hydroxyl, and R ²And R ⁴Be hydrogen.

5. the composition of any one, wherein Y, Y in the above claim ¹And Y ²Has general formula (CHR ⁸) _d, R wherein ⁸Be the alkyl or the hydrogen of 1～6 carbon atom, and d is 1～4 integer.

6. the composition of any one in the above claim, wherein m is 1, n is 5～10 integer.

7. the composition of claim 6, wherein the numerical value of m+n is 6 or 8, perhaps the numerical value that has a m+n at the mixture of this compound is 6 and 8.

8. the composition of any one, wherein R in the above claim ³It is the hydrocarbyl group of at least 8 carbon atoms.

9. the composition of claim 8, wherein R ³It is the alkyl group of 8～20 carbon atoms or by polyisobutene deutero-polymerization hydrocarbyl group.

10. the composition of any one, wherein R in the above claim ⁵Be hydrogen, and R ⁰(words of existence) are hydrogen.

11. the composition of any one in the above claim, wherein the content of ring compound is 5～1000ppm (is benchmark with the composition weight).

12. the composition of any one in the above claim, wherein jet fuel is a Merox fuel.

13. the composition of any one in the above claim, it also comprises hydroxycarboxylic acid, and it is different from described compound and has at least 1 chain of at least 8 carbon atoms.

14. the composition of claim 13, wherein hydroxycarboxylic acid is a beta-hydroxycarboxylic acids.

15. the composition of claim 14, wherein hydroxycarboxylic acid is the Serine that N-replaces.

16. the composition of claim 15, wherein hydroxycarboxylic acid is N-(polyisobutenyl succinyl-) Serine.

17. the composition of any one in the claim 13～16, wherein the weight ratio of ring compound and hydroxycarboxylic acid existence is 30～85: 70～15.

18. the composition of any one in the above claim, wherein this fuel is jet fuel.

19. a mixture that is used for liquid hydrocarbon fuels, it comprises the hydroxycarboxylic acid of any one defined in the ring compound of any one defined in the claim 1～10 and the claim 13～17.

20. one kind makes the fuel heat method of stabilizing that contains kerosene stock or contain jet fuel, it comprises that the mixture with the compound of any one defined in the claim 1～10 or claim 19 mixes with described fuel.

21. the mixture of the compound of any one defined or claim 19 defined is used to make the application that contains kerosene stock or jet fuel thermostabilization in the claim 1～10.